Polyglycol ethers suitable for detergent preparations, and process for preparing the same



United States Patent O ABSTRACT OF THE DISCLOSURE Non-ionic surfaceactive polyglycol ethers soluble in water at temperatures of at leastabout +5 C. and prepared by the addition of alkylene oxide onto highermolec- I ular weight saturated aliphatic hydrocarbon 1,2-glycol havingbetween about 8-26 carbon atoms in the molecule at a temperature ofbetween about 50-200 C. and at a pressure at least as high as normalpressure, and having turbidity points of between about -105 C.

This application is a streamlined continuation of US. application Ser.No. 297,221, filed July 24, 1963, now abandoned.

The present invention relates to polyglycol ethers suitable fordetergent preparations and a process for preparing the same, and moreparticularly to such polyglycol ethers which are suitable as non-ionicwash-active substances in wetting, washing, cleaning, and rinsingagents, in the form of alkylene oxide adducts of higher molecular weightaliphatic 1,2-glycols.

Water-soluble non-ionic surface-active or capillary active polyethersmay be manufactured generally by adding ethylene oxide onto alcohols ofhigher molecular weight which contain an aliphatic hydrocarbon radicalwith 8-20 and preferably about 10-18 carbon atoms in the chain. In thisconnection, not only have monovalent primary alcohols been used as thealcoholic starting material, but also diols have been proposed for thispurpose, wherein the hydroxyl groups are located approximately in themiddle of the carbon chain in question as adjacent secondary hydroxylgroups, as for example in the case of 9,10-octadecanediol. Moreover,diols have also been used in which one hydroxyl group is present as aterminal primary hyr droxyl group, while the other hydroxyl group islocated approximately in the middle of the carbon chain as a secondaryhydroxyl group, as for example, in the case of 1,12-octadecanediol.

It is an object of the present invention to provide polyglycol etherssuitable for detergent preparations, and a process for preparing thesame, especially polyglycol ether adducts of alkylene oxide with highermolecular weight aliphatic 1,2-glycols.

It is another object of the present invention to provide such polyglycolethers which are suitable as non-ionic wash-active components capable ofincreasing the wetting, washing, cleaning, and rinsing capacity ofsynthetic detergents of the organic wash-active sulfate and sulfonatetype. 69

Other and further objects of the present invention will become apparentfrom a study of the within specification and accompanying examples.

It has been found in accordance with the present invention thatpolyglycol ethers suitable for detergent preparations as well as aprocess for their manufacture may now be provided, the polyglycol ethersobtained having 3,406,208 Patented Oct. 15, 1968 ice especially goodtechnical and commercial usability characteristics. These polyglycolethers are produced by transforming terminal diols of higher molecularweight, i.e., 1,2-glycols, into water-soluble products by the additionof alkylene oxides.

Specifically, the present invention contemplates a process for theproduction of non-ionic surface-active polyethers of higher molecularweight diols, which comprises reacting alkylene oxide with highermolecular weight aliphatic 1,2-glycols having between about 8-26,preferably 8-22 and more preferably 10-18 carbon atoms in the moleculeat a temperature of between about -200 C. and at a pressure at least ashigh as normal pressure, and recovering the water-soluble polyalkyleneglycol ether adduct formed. Conveniently, a mixture of higher molecularweight diols may be used which contains at least about 1,2-glycolcontent. The alkylene oxide used may be ethylene oxide, or a mixture ofethylene oxide and one or more other alkylene oxides, such as propyleneoxide. Generally, the ratio of ethylene oxide to the other alkyleneoxide present, and especially propylene oxide, is between about 0.25-4:1, and more preferably between about 0.5- 2:1.

Optionally, the propylene oxide may be reacted with the 1,2-glycolfirst, and thereafter the ethylene oxide caused to react with theaddition product formed between the propylene oxide and 1,2-glycol, orthe ethylene oxide may first be reacted with the 1,2-glycol andthereafter the propylene oxide caused to react with the addition productpreviously formed. Moreover, the ethylene oxide and propylene oxide orother alkylene oxide may be reacted with the 1,2-glycol at the sametime.

In accordance with one embodiment of the invention, the 1,2-glycol usedcontains between about 10-18 carbon atoms in the molecule and thetemperature of the reaction is between about -180 C. while using acatalyst selected from the group consisting of acid and basic catalystsin an amount of between about 0.01-5% by weight based upon the1,2-glycol present.

Accordingly, non-ionic surface active polyglycol ethers soluble in waterat temperatures of at least about -|-5 C. may be provided by suchaddition of alkylene oxide on to higher molecular weight aliphatic1,2-glycols having be tween about 8-26 carbon atoms in the molecule at atemperature of between about 50-200 C. and at a pressure at least ashigh as normal pressure. Such polyglycol ethers may be made withethylene oxide or a mixture of ethylene oxide and propylene oxide in theaforesaid molar ratio of ethylene oxide:propylene oxide of between about0.25- 4:1.

The polyglycol ether adduct of alkylene oxide and higher molecularweight aliphatic 1,2-glycol having between about 8-26 carbon atoms inthe molecule, according to the present invention, should contain about0.13- 0.45 alkylene glycol ether radicals in the adduct for each carbonatoms present in the aliphatic 1,2-glycol radical, the adduct beingnon-ionic, surface active and watersoluble at temperatures of at leastabout plus 5 C. The adduct should also have a turbidity point of betweenabout 2010S C. and more particularly between about 35-65 C., especiallywhere the aliphatic 1,2-glycol contains about 10-18 carbon atoms in themolecule.

It should be noted that where the aliphatic 1,2-glycol contains betweenabout 8-14 carbon atoms in the molecule, the adduct should containpreferably about 2-3 ethylene glycol ether radicals. Where the aliphatic1,2- glycol contains between about 12-16 carbon atoms in the molecule,the adduct should contain about 3-4 ethylene glycol ether radicals. Onthe other hand, where the aliphatic 1,2-glycol contains between about16-20 carbon atoms in the molecule, the adduct should contain about 4-6ethylene glycol ether radicals. Generally, therefore,

where the aliphatic 1,2-glycol contains between about 8-20 carbon atomsin the molecule, the adduct contains about 2-10 ethylene glycol etherradicals.

Where the adduct contains ethylene glycol radicals and propylene glycolradicals, it will be appreciated that the propylene glycol radicals maystand in the. adduct between the aliphatic 1,2-glycol radical and theethylene glycol radical, or the ethylene glycol radicals and thepropylene glycol radicals may be present in the adduct in randomdistribution. Of course, the propylene glycol radicals may also be boundto the aliphatic 1,2-glycol radicals through the ethylene glycolradicals present. Actually, in accordance with one preferred embodimentof the invention, between about 1-12 propylene glycol radicals arepresent in the adduct and for each such proplyene glycol radical betweenabout 0.25-4 ethylene glycol radicals are also present, the total numberof ethylene glycol radicals present in the adduct also satisfying therequirement noted above that there be present at least about 0.13-0.45ethylene glycol radicals for each carbon atom present in the aliphatic1,2-glycol radical. The number of ethylene glycol radicals present maybe counted only once in determining the amount necessary to satisfyadditively the molar ratio range of 0.25-4 and the molar ratio range of0.13-0.45 per aliphatic carbon atom. In short, the number of ethyleneglycol radicals required for each carbon atom in the aliphatic1,2-glycol radical is to be added with the number of ethylene glycolradicals required for the number of propylene glycol radicals present.

Consequently, the present invention represents an improvement in adetergent preparation containing as wash active component at least oneof a synthetic organic wash active sulfate compound and a syntheticorganic Wash active sulfonate compound, which comprises includingtherein the non-ionic, surface active polyglycol ether adduct ofalkylene oxide and higher molecular weight aliphatic 1,2-glycols of thepresent invention as more fully described hereinabove. The adduct shouldbe present in an amount of at least about 65% by weight based upon thetotal quantity of adduct and wash active component in the detergentpreparation in question. The adduct should also be present in an amountof at least about 5% by Weight based upon the entire formulation of thedetergent preparation. Moreover, in accordance with one preferredembodiment of the invention a fatty acid ester sulfonate is included asthe wash active sulfate compound.

The detergent preparation may contain as wash active component suitablya member selected from the group consisting of synthetic organic washactive sulfate compounds, synthetic organic wash active sulfonatecompounds, and mixtures thereof in admixture with the nonionic, surfaceactive polyglycol ether adduct of the present invention. In this way thepresent invention represents an improvement in the process of increasingthe wetting, Washing, cleaning, and rinsing capacity of syntheticdetergents having organic wash-active compounds of the sulfate andsulfonate type, which comprises including the non-ionic surface-activepolyglycol ether adduct of the present invention in the detergentpreparation in question.

For the transformation of terminal glycols of higher molecular weight,i.e., 1,2-glycols, into water-soluble products by the addition ofalkylene oxides, terminal glycols may be used as starting materialswhich are obtainable from terminal aliphatic olefins having 8-26, andpreferably 8-22 carbon atoms in the molecule, and most particularly10-18 carbon atoms in the molecule. These olefins include octylene,nonylene, decylene, hexadecene, eicosene, docosene, etc. Such terminalolefins are obtainable in good yields and high concentrations by thecracking of parafiin hydrocarbons by appropriate methods, for example.Such olefin hydrocarbons are of an aliphatic nature, as the artisan willappreciate. The olefins may be straight-chain or branched-chainaliphatic olefins containing 8-26 carbon atoms, such as alkyl, includingoctyl-,

nonyl-, decyl-, hexadecyl-, eicosyl-, docosyl-, etc., e.g. ethylhexyl,propylhexyl, butylhexyl, etc. groups containing terminal olefinic orethylenic unsaturation, whereby in turn the corresponding C alkane1,2-di0ls Will be formed.

Specifically, the transformation of these terminal olefins into thedesired terminal glycols may be performed by various methods, such asfor examplethe process according to Swern, Journal of the AmericanChemical Society, vol. 68 (1946), pages 1504-1507, by transposition with"hydrogen peroxide and formic acid or acetic acid, followed byhydrolysis of the semiester that then develops. Nevertheless, theolefins can also be transformed to the 1,2- glycols by other methods,using hydrogen peroxide, as for example for transforming the olefinsinto terminal epoxies and hydrolyzing the latter to glycols, by theadding on of hypochlorous acid and the saponification of the resultingchlorhydrins, or also by direct oxidation of the olefins with the oxygenfound in the air according to the process of German Patent 734,838,which corresponds to the subject matter of US. Ser. No. 287,332, filedin 1939, now apparently abandoned.

The glycols produced as crude products by any one of the above-mentionedprocedures, preferably in a mixture with the starting olefins or thesaturated hydrocarbons accompanying the same, possess a substantiallyhigher boiling point than the hydrocarbons used for their manufacture.Hence, the hydrocarbons and glycols can be separated extensively bydistillation procedures, if the starting hydrocarbons were not fractionsof all the same C-number but rather were mixtures of homologs withoutexcessively great or broad ranges of C-number. Obviously, allowance mustbe made for the formation of azeotropes. If, on the other hand, mixturesof glycol and hydrocarbon having overlapping boiling ranges have to beseparated, the glycols and the hydrocarbons can be separated from oneanother by crystallization or extraction. In this regard, low aromatichydrocarbons, such as unsubstituted and lower alkyl substitutedarylhydrocarbons, including Irnonoand dilower alkyl substituted benzenehydrocarbons have proven to be good solvents for such recrystallization,especially benzene, toluene, and xylene.

According to the present invention, it is preferred that the 1,2-glycolsto be processed are higher percentage mixtures, i.e. in which at least75% by weight and more particularly by weight, and especially more thanby weight of 1,2-glycols are present, so that any hydrocarbons that mayexist in the final product will be comparatively unimportant. However,such residual hydrocarbons can still be distilled off, perhaps togetherwith any unreacted glycol that may be present.

For the transformation of the terminal glycols (i.e., saturatedaliphatic hydrocarbon 1,2-diols, or saturated aliphatic hydrocarbon1,2-glycols, e.g., produced by any of the aforesaid processes) intotheir non-ionic, surface active or capillary active, water-solublepolyglycol ethers, ethylene oxide is added on, which can be used aloneor together with other alkylene oxides, such as propylene oxide,butylene (butene) oxide, amylene (pentene) oxide, hexylene (hexene)oxide, heptylene (heptene) oxide, octylene (octene) oxide, etc. In thelatter instance, and especially where one of the higher alkylene oxidesis use-d and in particular propylene oxide, any desired order ofaddition of the alkylene oxides onto the 1,2-glycol may be used. Thus,the propylene oxide may be added on before the ethylene oxide, the oxideof ethylene and the propylene oxide may be used in admixture and thusadded on in random arrangement, or lastly, the ethylene oxide can beadded on first, and thereafter the propylene oxide. The same is actuallytrue for all alkylene oxides, and especially the lower alkylene oxides.In all cases, the quantity ratio of ethylene oxide to propylene oxide,or other higher alkylene oxide, is to be adjusted so that the polyethersobta-ined are still soluble at temperatures of at least about 20 C.,i.e. about ordinary or room temperatures. The

ratio of ethylene oxide to propylene oxide, or other higher alkyleneoxide, may range as aforesaid approximately between 4:1 and 1:4 (i.e.025-411) and preferably between 221 and 1:2 (i.e. 0.5-2:1). The additionof the alkylene oxide to the glycols in question is performed preferablyat elevated temperatures of 50-200 C. for example preferably betweenabout 80-180 C. at normal or elevated pressure as for example up toabout 25 atmospheres absolute or even higher. The reaction is generallyaccelerated by basic or acid catalysts.

Among the basic or alkaline catalysts which may be used are the metalssodium and potassium, or their hydroxides, or soaps, such as aliphaticor fatty acid soaps, and primarily their alcoholates such as aliphaticalcoholates and especially fatty alcoholates and most preferablyalkanolates. In addition to the preferentially used methylates, it isgenerally possible to use the aliphatic alcoholates of monovalent tohexavalent alcohols having 1 to 7 carbon atoms in the molecule.Significantly, however, the terminal glycols to be processed inaccordance with the present invention to form the desired products maythemselves be used as catalysts, i.e. in the form of their alcoholates,for instance, by dissolving free alkali metals, such as sodium and/orpotassium in them. The quantity of basic catalyst amounts toapproximately 0.01-5% by weight and preferably 0.05-0.5% by weight, ofthe alkali metal used with reference to the starting material, i.e.aliphatic 1,2- glycol.

On the other hand, the group of acid catalysts which may be used in thisconnection includes compounds such as boron trifiuoride, for example,which is usually used in the form of its addition compounds, and alsothe halides of zinc, iron or aluminum, such as the chlorides, bromides,iodides and fluorides of these metals, as well as the chlorides andbromides of tetravalent tin and pentavalent antimony. The acid catalystsare usable in approximately the same quantities as the basic or alkalinecatalysts, i.e. 0.01-5 by weight and preferably 0.050.5% by weight withreference to the starting material, i.e. the 1,2-glycol beingtransformed.

In the polyglycol ethers obtained in accordance with the foregoing, thepolyglycol ether chain is in all probability bound to the oxygen atom ofthe primary diol hydroxyl moiety, while the secondary diol hydroxylmoiety probably stands as a free hydroxyl group. However, there is noabsolute certainty as to the correctness of this assumption, and it mayalso be that at least a part of the alkylene oxides to be transposedwith the diol has reacted with the secondary diol hydroxyl. It will beunderstood in this connection that the present invention is not meant tobe limited to any specific theory of the linkages between the polyglycolether chains and the 1,2-glycol moieties.

Generally, the amounts of ethylene oxide to be added on or combined withthe 1,2-glycol in order to achieve water solubility are smaller than inthe case of fatty alcohols of equal chain length. Thus, two or three to10 mols of ethylene oxide are required per mol of glycol, depending uponthe C-number of the glycol used. Large amounts, of course, may also beadded, as much as 40 mols, for example, of ethylene oxide per mol of theglycol used. Of course, these figures can be larger in the case of mixedethylene glycol and higher alkylene glycol ethers, such as propyleneglycol ethers.

It will be realized that the minimum amount of ethylene oxide requiredfor the achievement of suflicient water solubility for surfactant usewill vary with the chain length of the diols to be processed. In thisregard, with the lower compounds of the series, such as diols having8-14 carbon atoms, the addition of 2-3 molecules of ethylene oxide perdiol molecule will suffice. On the other hand, where diols with 12 to 16carbon atoms in the molecule are concerned, products which are readilywater soluble are often achieved by the addition of only 3-4 mols ofethylene oxide. With the higher members of the series, i.e. those having16-20 carbon atoms in the molecule, somewhat more ethylene oxideobviously has to be added on for the desired purpose, as for example 4-6mols thereof. Indeed, products are also usable which contain even largeramounts of ethylene glycol ether radicals in the molecule, as forinstance those having more than 10 and up to 20 ethylene glycol etherradicals. In general, unless the radicals of higher glycols are presentin the molecule, such as propylene glycol or butylene glycol, etc., itis not necessary to go beyond 10 ethylene glycol ether radicals, and inthe case of compounds containing up to 16 carbon atoms in the diolradical not beyond 6 ethylene glycol ether radicals, in order to achievethe desired surface active or capillary active water solublecharacteristics desired.

Generally, where no propylene glycol radicals are present in the diolpolyglycol ether product of the present invention, the total number ofethylene glycol radicals present therein should be at least 1, suchtotal number also satisfying the requirement that 0.1-0.7, preferably0.12-0.55, and more preferably 0.13-0.45 ethylene g ycol radicals bepresent for each carbon atom of the diol radical. Where the productcontains additionally propylene glycol radicals, i.e. in an amount offrom 1-12 .per diol molecule, an additional amount of ethylene glycolradicals to the aforesaid total number must be present. In the lattercase, the combined total number of ethylene glycol radicals which mustbe present in the product includes (1) the total calculated on the basisof the number of carbon atoms in the diol radical and (2) the amountnecessary on the basis of the number of propylene glycol radicalspresent in accordance with the aforesaid ratio of 0.25-4, preferably0.5-2 ethylene g ycol radicals per propylene glycol radical.

If the new diol polyglycol ethers of the present invention are to beused as wetting agents and detergents, or in detergent preparations, endproducts are selected Which possess a degree of ethoxylation that theturbidity points will lie approximately in the range of the applicationtemperature for the agents and/ or detergent preparations, or,preferably somewhat higher than the application tem- :perature. Ifaqueous solutions of the diol polyglycol ethers are to be used attemperatures ranging from 15 to 25 C., for example, polyglycol ethershaving tubidity points of at least 20-35 C. should be used, whereas ifthe application temperature for the products in question ranges from 30to C., it is expedient and appropriate to use polyglycol ethers havingturbidity points of 35-55 C. Moreover, if the application temperaturelies in the range of -100 C., it is expedient to select products havingturbidity points of from -105 C. All of the foregoing temperature dataand requirements actually mean that the amount of surface activepolyglycol ether which is adequate for the intended effect shouldpossess a higher turbidity point than the application temperatureinvolved for the particular product. This should be true in general ofat least 50%, preferably more than and especially 100% of the amount ofthe diol polyglycol ether in question, for example where the detergentpreparation being used at a particular application temperature containsa mixture of diol polyglycol ethers, some of which have a higherturbidity point than others for the particular application temperaturein question.

Nevertheless, the polyglycol ethers to be used in accordance with thepresent invention may in part possess lower turbidity points, thepercentage of these being the difference between the above-statedpercentage and The lower turbidity points may be attributed toincomplete ethoxylation or to the presence of propylene or bu'tyleneglycol radicals, and/or higher alkylene glycol radicals, in themolecule, which latter radicals are not as effective for the desiredpurpose at least on a one for one comparison basis with ethylene glycol.Any such compounds, whose turbidity point may be as low as +5 C., butwhich is preferably between 5-10 C., and especially between 10-20" C.,need not interfere with the 7 use of the more water soluble diolpolyglycol ethers in practice at the application temperature involved.

Advantageously, the aqueous solutions of the surfaceactive diolpolyglycol ethers in accordance with the present invention are suitablefor the treatment of the surfaces of any kind of solids and thistreatment can be performed in industrial or commercial operations, oralso under household conditions. These applications include, forexample, all kinds of textile treatments, especially washing, and thetreatment, and especially the cleaning, of surfaces of solids other thantextiles, such as metal, wood, ceramic products, such as porcelain,especially porcelain dish ware, plain tiles, glazed tiles, and glass.Plastics and lacquered and polished surfaces can also be treated withthe aqueous solutions of the diol polyglycol ethers of the presentinvention. In particular, with respect to the rinsing of dishes, whichmay be performed by hand or in the more or less automatic operatingapparatus now available, such as dish washers, the aqueous solutions ofthe diol polyglycol ethers in question produce a good draining effect,which is apparent both with dish ware of ceramic materials as well aswith plastic dish Ware and metals. The rinsing liquid wets the entiresurface of the dish ware, drains evenly away and dries withoutstreaking. This effect can also be exploited, of course, in the case ofall other kinds of industrial and commercial treatments of metal orother substances.

The advantageous properties of the new diol polyglycol ethers can beobserved etfectively not. only when they are used in the form of theiraqueous solutions without any additives, but also when used with theusual additives, the nature of which will depend upon the applicationunder consideration.

Thus, as non-ionic surfactants, the diol polyglycol ethers of thepresent invention are compatible both with acids and with alkalis andtherefore they can be combined with acids, salts of acid, neutral ororganic reaction, and bases as well. The pH values of the aqueoustreating solutions containing surface active diol polyglycol ethers ofthe present invention may range from 1 to 12, depending upon theirintended application. The acid pH range is desirable primarily for manypurposes in the treatment of metals, such as acid cleaning of metals,economical pickling, etc. Fine detergents, rinsing agents, and cleansersfor household use may also be included and these are generally almostneutral to weakly alkaline, i.e., their aqueous, ready-for-use solutionshave pH values ranging from 69 and preferably 7-8.5. The aqueoussolutions of strong detergents generally have higher pH values, as forexample from 9-115 and preferably from 9.5-l0.5. Solutions which arestill more strongly alkaline, having pH values from 11-12, are importantfor the cleaning industry in particular, and more specifically in thefood industry, such as in the beverage industry, the dairy industry,etc. where the containers must be scrupously cleaned before use.

Acid substances which are suitable for use together with the diolpolyglycol ethers of the present invention include the usual organic orinorganic acids or acid salts, including the alkali and ammonium salts,such as hydrochloric acid, sulfuric acid, bisulfates of the alkalies,aminosulfonic acids, nitric acid, orthophosphoric acid or other acids ofphosphorous, especially the anhydrous acids of phosphorus, i.e.metaphosphoric, and pyrophos- 'phoric acids, etc. or their acids salts,especially the alkali and ammonium salts, or their acid reacting solidcompounds with urea or other low carboxylic acid amides, partial amidesof phosphoric acid, or of the anhydrous phosphoric acids, citric acid,tartaric acid, lactic acid, oxalic acid, etc.

The approximately neutral or weakly alkaline or strongly alkalinetreating liquids which may be used in accordance with the presentinvention may contain the additives customarily used in washing,cleaning, and rinsing preparations, together with surfactants. Theseadditives include not only neutral salts, such as sodium sulfate, whichis able to improve the eifectiveness of the wash active component evenwhen used alone, but also wash active alkali reacting salts, such as thealkali carbonates and bicarbonates, water-soluble. alkali silicates,alkali orthophosphates, etc., which are most preferred and especiallysodium carbonate, disodium phosphate, trisodium phosphate, etc.Moreover, the additives may also contain anhydrous-phosphates includingthe pyrophosphates, which insofar as they do not contain any hydrogenatoms replaceable by metals are sufliciently alkaline to serve aswash-active alkalies, and the polyphosphates, such as, for exampletripolyphosphate Na P O and tetrapolyphosphate Na P O Thepolymetaphosphates are also usable in this connection, although suchmetaphosphates in polymeric form because of their slightly'acid reactionshould be employed only at most in such quantities that the alkalinereaction of the other components of the de tergent is not counteracted.Conveniently the slightly acid-reacting metaphosphates may be employed,for example, in the production of fine wash agents for the purpose ofstandardizing the lower pH values. In this connection. the acidorthophosphates or pyrophosphates noted above may also be used forstandardizing the pH values of the detergent preparation as well as theweak inorganic or organic acids or acid salts of strong organic acids,such as boric acid, citric acid, oxalic acid, lactic acid, glycolicacid, tartaric acid, sodium bisulfate, etc.

The usual organic chela-te formers may also be present in the detergentpreparations in accordance with the present invention, these chelateformers often being derivatives of monoor poly-amines, wherein the basicnitrogen atoms are substituted with lower radicals containing carboxylor hydroxyl groups. This is especially true with respect to carboxyl orhydroxyl groups of an aliphatic or cycloaliphatic nature having from 1to 6 carbon atoms, with a plurality of such radicals being able to bebound to one nitrogen atom. Examples of such substances include:ethylene diaminotetraacetic acid, nitrilotetraacetic acid,monohydroxyethyl ethylenediamine-triacetic acid, etc.

In addition to the foregoing, in accordance with the present invention,the known per compounds may be included in the detergent preparations inquestion, such as the hydroperoxides of sodium boratc, alkalicarbonates, alkali-orthophosphates, alkali pyrophosphates, alkali polyphosphates, etc. Of course, stabilizers may be used together with theseper compounds, and the same may be water-soluble or water-insoluble. Inthe case of watersoluble stabilizers, these include, in addition to theabovementioned complex formers, dipicolinic acid, quinaldinic acid,quinolinic acid, and acylation products of phosphoric acid, for exampleaccording to German Patent 1,107,207, which substantially corresponds tothe products disclosed in US. application Ser. No. 29,778, filed 1960and Ser. No. 170,221, which represents a continuation-impart applicationthereof. On the other hand, the water-insoluble stabilizers includevarious very finely divided, large-surface solids, such as silicic acid,alkaline earth silicates produced by precipitation, especially magnesiumsilicate, and also meta-stannic acid and the like.

The effect of the per compounds can be intensified effectively by thecustomary activators, such as, for example, small amounts of heavy metalions, especially copper ions. Since such ions, however, act as catalystsfor the decomposition of the per compounds, the same cause anundesirably rapid evolution of oxygen, and therefore such activatorshave to be applied in bound form. Specifically, the activators may beused together with an excess quantity of complex formers, such as theabove-mentioned chelate formers, or with large-surface substances likemagnesium silicate, metastannic acid, etc. In this connection, aparticular combination of magnesium silicate, small amounts of copperand aminopolycarboxylic acids has proven to be a good activator. Also,organic sub- 9. stances have proven to be usable advantageously asactivators, such as benzoic acid anhydride, other carboxylic acidanhydrides, propiolactone and other beta-lactones, etc.

The surface-active diol derivatives to be used according to the presentinvention, i.e. which possess a lower sudsing ability than that of manyanionic wash-active substances, can be used advantageously together withsubstances which influence the sudsing ability of their aqueoussolutions. With these anionic wash-active substances, the preparationsare especially suitable as wash-active substances in machine laundrying,as for example in household automatic washing machines. Of course, itmay be desirable to reduce the sudsing ability even further. To thisend, the foaming diol-ethyleneglycolethers of the present invention canbe combined, as generally described in German application 1,135,122,which corresponds with US. application Ser. No. 99,650, filed 1961, andUS. application Ser. No. 276,983 which is a continuation-in-partthereof, with non-ionic products in which the end of the polyethyleneglycol chain opposite the hydrophobic radical contains polypropyleneglycol radicals which reduce the water-solubility. The hydrophobicradical may also originate from 1,2-diols.

Furthermore, inorganic or organic colloid substances,water-soluble-substances of higher molecular weight, etc. can beincluded as additives in the preparations in accordance with the presentinvention, these colloid substances serving as dirt carrier in thewashing process. In general, the colloids improve the dirt-carryingcapacity of the synthetic wash-active substances used and such colloidsinclude, among others, water-soluble salts of polyacrylic acid orpolymethacrylic acid, water-soluble salts of polymeric carboxylic acids,glue, gelatin, salts of ether carboxylic acids, or ether sulfonic acidsof starch or cellulose as well as salts of sulfuric acid esters ofcellulose or starch, and especially carboxymethylcellulose, ethers ofcellulose and hydroxyalkylsulfonic acids as well as cellulose sulfates,and the like.

As synthetic wash-active substances which may be used in accordance withthe present invention in the detergent preparation in question, theseinclude any of the wellknown anionic capillary active or wash-activesubstances having hydrophobic radicals, as for example, a straight chainor branched chain, saturated or unsaturated aliphatic hydrocarbonradical having 8 to 22 and preferably 10 to 18 carbon atoms, andwater-solubilizing groups of the sulfate or sulfonate type so as tolower the surface tension of the water or aqueous washing solution.Among the substances specifically contemplated are the alkyl sulfonates,the alkyl benzene sulfonates, fatty acid sulfonates, salts, esters,etc., fatty alcohol sulfates, and olefin sulfonates, as well as fattyalcohol glycerin ether sulfates, fatty alcohol polyglycol ethersulfates, fatty acid monoor diglyceride sulfates, etc. The hydrophobicradical, of course, may also be connected with a sulfonate or sulfategroup by means of a phenyl radical and/ or a hetero atom, such as anintermediate member containing ether oxygen atoms. This is illustrated,for example, by the alkyl benzene sulfonates, sulfo-succinic acidesters, or other sulfodicarboxylic acid esters, tetrapropylene phenylethyl sulfates, alkylphenoxy ethyl sulfates or alkylphenoxy polyalkyleneglycol sulfates, fatty alcohol glycerin ether sulfonates, having, forexample 110 and preferably 1-5 polyethylene glycol moieties in themolecule, fatty acid monoor di-glyceride sulfates, fatty acid alkylolamide sulfates, etc. The foregoing substances are generally known andneed not be defined in any detail as will be appreciated by the artisan.

In the preparation of aqueous detergent solutions, in accordance withthe present invention, the surface-active diol derivatives in questionand any additives of the foregoing type which are to be used may bedissolved in the water content either simultaneously or in any desiredorder. It is possible also, however, to use ready made or alreadyformulated preparations such as solids which already contain all of thesubstances required for the particular purpose. Generally, however, theready-made preparations can be used as concentrates in liquid or pasteform, or else in the form of solids, such as pourable granularsubstances, including more or less fine powders, granulates, oragglomerates as well as in shapes obtained in some particular manner,such as flakes, ribbons, needles, etc.

. In any case the formulations making up the detergent preparationsshould be adjusted so that the desired pH will be obtained in thewashing solution to be utilized, the pH generally being determined withrespect to a 1% solution of the washing agent, whereby, depending uponthe demands made on the detergent preparation, pH values between 1 and12 are possible. 1

The aliphatic 1,2-glycol ethers obtained in accordance with the presentinvention may also be present as nonionic wash-activ or capillary activesubstances in pourable and sprinklable form, and especially powdereddetergents, wetting agents and emulsifiers, i.e. which additionallycontain surface-active salts of sulfo fatty acid esters and salts ofsulfo fatty acids having 10 to 24 and preferably 12 to 18 carbon atomsin the molecule, It will be realized, nevertheless, that the percentgeof the aliphatic 1,2polygl:ycol ethers of the present invention shouldbe at most about 65% by weight with reference to the mixture of the1,2-p0lyethylene glycol ether and surface-active ester salt in question.Of course, where the diol polyglycol etders of the present invention arused as wetting agents, detergents, cleansers, and rinsing agents, theymay also be used in greater percentages than 65 by weight, as well aswithout any of the abovementioned surface-active salts of sulfo fattyacid ethers and sulfo fatty acids being present whatsoever.

Because of the oily to pasty consistency and the property of not gellingor not gelling so strongly when water is added, as is the case with thesurface-active fatty alcohol polyglycol ethers derived from monovalentalcohols, the products according to the present invention are especiallysuited for the production of liquid to pasty preparations into whichcommon or usual attendant substances can also be worked. In thisconnection, if substantially monophase, practically clear, solutions aredesired, the substances to be worked in are used in easily soluble form.For example, the wash active alkalies or other additives can be used inthe form of their readily soluble salts, i.e. sodium or potassium saltsor amine salts, especially the alkylolamines. Of course, it is possibleto use a plurality of the above-mentioned cations, for instance, sodiumand potassium salts may be used together, or potassium salts andtriethanolamine salts may be ued together or sodium and potassium andtriethanolamine salts may all be .used together, etc.

Furthermore, known solubilizers can be worked into the detergentpreparations in question, these including not only water-soluble organicsolvents, but also the so-called hydrotropic substances on the order ofthe lower arylsulfonates, such as toluene or xylene sulfonates. Ofcourse, these substances may also be present in the form of their sodiumand/0r potassium and/or alkylolamine salts. Furthermore, suchwater-soluble organic solvents are especially usable as solubilizerswhere the same have =boiling points above about 75 C., such as theethers of similar or different polyvalent alcohols or the partial ethersof polyvalent and monovalent alcohols such as the alkylols. Morespecificaly, these include, for example, dior triethylene glycol,polyglycerins and the partial ethers made up of ethylene glycol,propylene glycol, or glycerin and aliphatic, monovalent alcoholscontaining 1 to 4 carbon atoms in the molecule.

Although the solubility ow the water-soluble solids contained in theconcentrates in question can be increased by the above-describedmethods, the artisan is often faced with the problem of preparingconcentrates having such a degree of concentration that clear solutionscan no longer be produced despite the availability of the methods notedabove. In such cases, there are several ways of arriving at stablesuspensions in which the suspended substance practically do not settleout or at least can be shaken back easily into suspension. The settlingtendency decreases as the particle size of the solids correspondinglydecreases, as the difference in the specific gravities of the liquid andof the solid therein suspended decreases, and as the viscosity of theliquid increases. Even by means of a substantial reduction in theparticle size of the suspended solids, it is possible to obtain usableproducts herein. For instance, it has been proposed to prepare athixotropic liquid detergent by providing for a sufficiently smallparticle size in the tripolyphosphate to be incorporated into suchliquid detergent in solid form. If the solids are of the kind thatcrystallize, i.e. absorbing water of crystallization, then it isrecommendable to prevent this from happening by the addition ofalcohols, especially polyvalent aliphatic alcohols, such as glycols orglycerin or their partial ethers. At the same time, an increase in thespecific gravity of th liquid is also achieved as well as a certainincrease in viscosity, whereby the over-all stability is improved aswell.

To increase the viscosity, it is also recommended to add higherpolyglycol ethers or polyglycerins or other watersoluble substances ofhigh molecular weight, such as those'indicated above as dirt-carryingsubstances.

In spite of the oily to pasty consistency of the aliphatic1,2-polyethylene glycol ethers obtainable in accordance 'with thepresent invention, the same can be transformed into powders by the usualmethods. Specifically, these methods include, for instance, the bindingof the water present in an aqueous solution of the diol polyglycolethers in question by means of calcined salts which clystallize and bindwater of crystallization. In another method, the diol polyglycol ethersof the invention are absorbed by finely divided calcined salts, such asthose obtained in a very voluminous state, in some cases, by thedehydration of the salts containing water of crystallization. Soda madeby the heating of sodium bicarbonate can be used for this purpose aswell as fine-grained, voluminous anhydrous phosphates which weigh lessthan 550 grams per liter. Still another method that can be used for thepro duction of preparations in accordance with the invention consists inpreparing a fluid slurry of the diol polyglycol ethers in question andhydratable inorganic salts, then stirring and bubbling air through themixture until semisolid particles have formed, and thereafter allowingthe mixture to stand until a solid, friable mass has developed ofapparently dry, coherent, spherical, agglomer- -ated granules, andfinely breaking up such mass into granules.

The following examples are set forth for the purpose of illustrating thepresent invention, and it will be understood that the invention is notto be limited thereby:

Example 1 In order to form the addition product, a starting material wasused which consisted of octadecanediol-l,2, which had been madeaccording to Swern, Journal of the American Chemical Society," Vol. 68(1946) page 1504 to 1507, from a terminal octadecene, by transposi tionwith hydrogen peroxide and formic acid, followed by hydrolysis of thediol semiester that first develops. The octadecene-l used to form thediol is a commercial product made by the cracking of paraffin wax,having a terminal olefin content of about 97%. The rest consisted inpart of non-terminal olefin or of paraffin. The octadecanedioll,2 waspurified by distillation B.P. 178-l84 C./0.5 mm. Hg) and had a hydroxylnumber of 392.

The ethoxylation of this product was performed in a three-necked flaskequipped with a heating device, a contact thermometer, an agitator and agas inlet and outlet tube. To 95.3 grams of the above-describedoctadecanediol, 3.5 grams of a methanolic solution of sodium meth ylate(10% by weight Na) were added, and the mixture was heated to -130 C. Themethanol then was removed by evacuating the fiask three times followedeach time by scavenging with nitrogen. Then, beginning at a temperatureof 166 C., 89 grams of ethylene oxide gas were passed through theingredients in the flask. The heat of reaction raised the temperaturerapidly at first to 176 C., but thereafter the temperature was held bycooling to about C. After the above-stated amount of ethylene oxide hadbeen passed through the ingredients in the flask, the weight increaseamounted to 88.3 g. The reaction product was washed five times, eachtime with 200 cc. of 5% hot sodium sulfate solution. The water releasedwas removed under vacuum at 150 C. and the separated sodium sulfate wasfiltered off. A yield of 164 grams wasobtained of a polyglycol etherWhich contained about 6 mols of ethoxyl radicals per mol of diol. Thehydroxy number of the product was 194 and it dissolved in water at 35-40C. A 1% aqueous solution thereof had a turbidity point of 90 C.

Example 2 In accordance with the procedure described in Example 1, 30grams of oetadecanediol described in Example 1 were ethoxylated in thesame apparatus. To this end, 3 g. of a methanolic solution of sodiummethylate (10% by weight Na) were added and the methanol was driven oif.After scavenging out the gas space, with nitrogen, the passage ofethylene oxide (124 g.) through the mixture was begun. Since theabsorption of the ethylene oxide at C. was slow at first, thetemperature was increased to 175-185 C. and the reaction was continuedfor 230 minutes. After an overnight interruption, the balance of theethylene oxide was fed in within 70 minutes at 161-176 C. The weightincrease then amounted to 122 g. After Washing, drying and filtering,the yield was 114 g. On the basis of the weight increase, a content of26 ethylene glycol radicals is calculated per molecule ofoctadecanediol. The hydroxyl number of the solid product obtained was79.1.

Example 3 The starting material in this case was a mixture of terminaldiols with 14 to 16 carbon atoms in the mole cule, which had beenproduced from an appropriate olefin in the manner described inExample 1. The diol mixture had a boiling range of 159220 C. at 0.1 mm.Hg and a hydroxyl number of 397.

In accordance with the procedure of Example 1, 4.6 g. of a methanolicsolution of potassium methylate containing 5% by weight potassium(calculated as the free metal) were added to 87 g. of the above diol.After driving off the methanol in the above-described manner, 71.5 g.ethylene oxide were passed through the mixture within 120 minutes,beginning at a temperature of 155 C. At the initiation of the reaction,the temperature first rose to 160 C. and was then held at about 150 C.by cooling. The yield amounted to 142.4 g. An average content of 4.9ethyleneglycol radicals is calculated from the weight increase. Thehydroxy number of the product amounted to 220. The turbidity point of a1% aqueous solution was 80 C.

Example 4 The starting material was a tridecanediol-1,2, which had beenobtained from the corresponding olefin by transforming the latter to theepoxy form, transposing the epoxy with acetic acid anhydride to form theglycoldiester, and cleaving the latter. The tridecanediol passed over inthe distillation in the range of 127128 C./0.05 mm. Hg and had a hydroxynumber of 511.

In accordance with the procedure of Example 1, 110 g. of thistridecanediol were heated to 100 C. in the apparatus described above and0.3 g. of metallic sodium was added. After the sodium had dissolved, thetempera- 13 ture was raised to 160 C., and, after scavenging theapparatus, with nitrogen, ethylene oxide was passed through until theweight increase amounted to 93 grams. The reaction product was washedfive times at 90 to 100 C. with 400 cc. of 5% sodium sulfate solutioneach time, freed of water under vacuum at 130-150 C., and filtered whilestill hot. The yield amounted to 178.5 grams. The hydroxyl number of theproduct was 278. On the basis of the ethylene oxide absorption, acontent of 4 glycol ether radicals per molecule is calculated. Theturbidity point of the product in a 1% aqueous solution was 65 C.whereas in a 1% solution of the product made with a 5% sodium chloridesolution, the turbidity point was 42.5 C.

Example 5 The starting material was a pentadecanediol-1,2, which hadbeen produced from the corresponding olefin in a manner similar to theone described in Example 1. However, the quantity of formic acid used inthat example was replaced by 1.15 times its volume of acetic acid, andfurthermore a small amount (0.57% of the volume of the acetic acid used)of concentrated sulfuric acid was added. The diol obtained was purifiedby distillation and passed over at 144150 C./ 0.05 mm. Hg. It had ahydroxyl number of 431.

Under the same conditions as described in the preceding example, 52grams of the pentadecanediol-1,2, thus obtained were treated bydissolving 0.2 g. of metallic sodium therein, and ethoxylated at 160 C.until 51 grams of ethylene oxide had been absorbed. The reaction productwas washed 3 times at 90 to 100 C. with 200 cc. of 5% sodium sulfatesolution each time. The yield was 94 g. The product obtained had ahydroxyl number of 229 and contained, on the basis of the ethylene oxideabsorption, 5.4 glycol ether radicals in the molecule. The turbiditypoint in 1% aqueous solution was 82 C., whereas in a solution of 1% ofthe product in a 5% sodium chloride solution, it had a turbidity pointof 58 C.

Example 6 Using an addition product of 4.5 mols of ethylene oxide ontoone mol of a terminal aliphatic diol mixture with 11 to 18 carbon atomsin the molecule, prepared in accordance with the procedure of Example 1,liquid preparations of the following composition were produced:

(a) 6% by weight adduct: diol mixture+ethoxyl 16% by weight sulfatedaddition product of 2 mols ethylene oxide and 1 mol of a C1244 fattyalcohol mixture (sodium salt).

Balance, water.

(b) 16% by weight adduct: diol mixture+ethoxyl 11% by weighttetrapropylene benzenesulfonate (triethanolamine salt) 7.5% by weightadduct: diol mixture-l-ethoxyl 7.5 by weight tetrapropylenebenzenesulfonate (sodium salt) Balance, water.

(d) 11% by weight adduct: diol mixture+ethoxyl 4% by weighttetrapropylene benzenesulfonate (triethanoL salt) Balance water.

(e) by weight adduct: diol mixture+ethoxyl 12% by weight sulfatedaddition product of 2 mols ethylene oxide and 1 mol of a C1244 fattyalcohol mixture (sodium salt) 13% by weight tetrapropylenebenzenesulfonate (sodium salt) 6.5% by weight tetrapropylenebenzenesulfonate (triethanolamine salt).

5% by weight ethanol Balance, water.

Example 7 In order to produce a powdered detergent having the followingcomposition, expressed in percentages by weight of the dry substance:

20% of an addition product of 4.5 mols ethylene oxide and 1 mol of aC1045 diol mixture 2% carboxymethylcellulose 40% sodium pyrophosphate10% Na 0.3.3 SiO 28 pentasodium tripolyphosphate,

an aqueous suspension containin the pyrophosphate, the polyglycol etheradduct, the alkali silicate and the carboxymethylcellulose istransformed by spray drying into a powder with a residual water contentof 7 to 10% by weight. This powder is mixed immediately after itsmanufacture with a highly voluminous tripolyphosphate having a bulkweight of about 400 grams per liter to provide the desired powdereddetergent preparation.

What is claimed is:

1. Non-ionic surface active polyglycol ethers soluble in water attemperatures of at least about +5 C. and prepared by the addition ofethylene oxide onto an alkane 1,2-diol having between about 8-26 carbonatoms in the molecule at a temperature of between about 50-200 C. and ata pressure at least as high as normal pressure and in the presence of acatalyst selected from the group consisting of sodium, potassium, sodiumhydroxide, potassium hydroxide, fatty acid soaps, alkanolates containing1-7 carbon atoms, alcoholates of C alkane 1,2- diols, boron trifluoride,zinc halides, iron halides, aluminum hralides, tin tetrachloride, tintetrabromide, antimony pentachloride and antimony pentabromide, in anamount of between about 0.015% by weight based on the 1,2-diol, about0.1-0.7 ethylene oxide ether radicals being present for each carbon atompresent in the alkane 1,2-diol radical, at least one mole of ethyleneoxide ether radical being present per mole of alkane 1,2- diol.

2. Non-ionic surface active polyglycol ethers according to claim 1,soluble in water at temperatures of at least about +5 C. and prepared bythe addition of ethylene oxide onto alkane 1,2-diol having between about10-18 carbon atoms in the molecule at a temperature of between about-180 C. and at a pressure at least as high as normal pressure, about0.1-0.7 ethylene oxide ether radicals being present for each carbon atompresent in the alkane 1,2-diol.

3. Polyglycol ether according to claim 1 constituting an adduct ofethylene oxide and alkane 1,2-diol containing eighteen carbon atoms andprepared by reacting one mole of said alkane 1,2-diol with 6 moles ofethylene oxide.

References Cited UNITED STATES PATENTS 2,828,345 3/ 1958 Spriggs 260-6152,934,568 4/ 1960 Barker 260-615 2,742,436 4/ 1956 Jenkins 252-1612,744,874 5/1956 Fife et al 252-161 1,970,578 8/1934 Schoeller et al.260-615 XR 2,714,761 10/1939 Schuette et al. 260-615 XR 2,457,139 12/1948 Fife et al. 2,425,845 10/ 1947 T oussant et al 260-615 2,674,619 4/1954 Lundsted 260-615 XR 3,030,426 4/ 1962 Mosely et a1 260-6153,036,118 5/1962 Jackson et al. 260-615 RX 3,053,903 9/ 1962 Holland260-615 3,119,848 1/1964 Wrigley et al. 260-615 XR FOREIGN PATENTS736,991 9/1955 Great Britain.

757,309 9/1956 Great Britain.

796,508 6/ 1958 Great Britain.

LEON ZITVER, Primary Examiner. H. T. MARS, Assistant Examiner.

U.S. DEPARTMENT OF COMMERCE PATENT OFFICE Washington, D.C. 20231 UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,406,212October 15, 1968 Karl O. Christe et a1.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 3, line 10, after "the" insert carbonyl chloride.

The reactants in the reactor vessel are Signed and sealed this 7th dayof April 1970.

(SEAL) Attest:

Edward M. Fletcher, Jr.

Attesting Officer Commissioner of Patents WILLIAM E. SCHUYLER, JR.

